Process for preparing 4,11-dichloroquinacridone pigments



Dec. 15, 1970 A. P. WAGENER ErAL PROCESS FOR PREPARING 4,Jl-DICHLOROQUINACRIDONE PGMENTS Filed Aug. 7, 1967 D .mllll'l ,41h34 1| mwIa OMZOCLOZOU m Udn m MZ4JQN M .Z .vom m .vwd Nm. No# O m. N .m N.v .m m m.m m .m M ...v who o.; M ,.I .NOMI NTM. mmm @www 8.# Oem m #o6 n. m oww OH I l ...si Ov om r. om ca .L S N a .L N i INVENTORS AN-l-HONYl P WAGENER GEORGE MEISTERS BY [A] ATTORNEY United States Patent O 3,547,928 PROCESS FOR PREPARING 4,11-DICHLOR- QUINACRIDONE PIGMENT S Anthony P. Wagener, Park Forest, and George J. Meisters,

Chicago, Ill., assignors to The Sherwin-Williams Company, Cleveland, Ohio, a corporation of Ohio Filed Aug. 7, 1967, Ser. No. 658,890 Int. Cl. C07d 39/00 U.S. Cl. 260-279 9 Claims ABSTRACT 0F THE DISCLOSURE This invention comprises a new 4,11-dichloroquinacridone pigment and the method of preparing said pigment by milling the crude compound with a solid, soluble inorganic salt at approximately 50-100o C. in the presence of pyridine or a homolog thereof. This new phase of the compound is distinguished by its red-orange color and characteristic X-ray diffraction pattern. This product has an X-ray diffraction pattern having lines of strong intensity at interplanar spacings of 4.06 and 3.45 Angstrom units, lines of intermediate intensity at 6.80, 5.00 and 3.35 A,. and Weak lines at 7.80, 6.21, 6.04, 5.38, 3.12 and 3.02 A. Its red-orange color is characterized by a dominant wave length of 604.5, alight purity of 92.0%, and a reflectance, orY value, of 17.05 at 100% pigment.

This application relates to a new 4,11-dichloroquinacridone pigment. More specifically it relates to a particular 4,1l-dichloroquinacridone pigment conditioned to givel a distinctive red-orange color and to impart a characteristic X-ray diffraction pattern. Still more specifically, it relates to a process for preparing such pigments by conditioning the crude compound by the step of milling it with salt at a moderately high temperature in the presence of pyridine or a homolog thereof.

4,11dichloroquinacridone is described in the patent literature, namely British Pat. 896,916, (1962), Belgian Pat. 618,873 (1962), U.S. Patent 3,985,023 (1963), and Imethods of preparation have also been disclosed, see U.S. Patent 3,107,248 (1963) and U.S. Patent 3,264,297 (1966). Two forms of this compound, namely alpha and beta, have been defined by X-ray diffraction spectra in U.S. Patent 3,160,510 (1964). The alpha has a very yellowish orange color and the beta is a very reddish orange.

This compound has the structural formula:

In accordance with the practice of this invention, it has now been found that 4,11-dichloroquinacridone of either the alpha or beta type, as well as mixture thereof, can be converted to a new red shade of orange pigment having a new characteristic X-ray diffraction pattern by the steps of milling the compound with salt of 50-100 C., preferably about 90 C. in the presence of pyridine or a homolog thereof, and thereafter recovering the red shape orange pigment product from the salt and the pyridine, etc.

'Ihis new pigment has a diffraction pattern characterized by a line of strong intensity of interplanar spacing at 4.06 Angstrom units, lines of intermediate intensity at 6.80, 5.00 and 3.35 A., and lines of weak intensity at 7.80, 6.21, 5.38 and 3.12 A., in addition to the various lines that are found in other phases of this compound. It also has a color defined by its tristimulus value as described hereinafter.

FIG. 1 represents graphically, the X-ray diffraction pat- ICC tern of this compound in the form produced by the process of this invention, together with the corresponding curves for the alpha and beta phases of this compound.

In preparing the new phase of this compound described herein, the crude' compound, in either its alpha or beta form, or mixture thereof, is milled with sodium chloride or other solid inorganic salt and pyridine or a homolog.

The inorganic salt used in the process of this invention can be of various types. Obviously it must be stable against decomposition at the temperatures used for the grinding operation and should be soluble in water or dilute acid so as to be easily removable from the dichloroquinacridone. Advantageously it should be one not having water of hydration which will be liberated during the grinding proce'ss. Because of its inexpensiveness and availability, sodium chloride is preferred. However, other salts such as potassium chloride, ammonium chloride, ammonium sulfate, sodium sulfate, calcium carbonate, etc. can be used. These can be of commercial grade, and any absorbed moisture present can be removed by prelieating the' salt separate from the quinacridone prior to its use.

The proportion of salt to pigment can be varied widely, ranging from 4 to 20 parts of salt per part of pigment. Very satisfactory results are obtained with about 9-10 parts o'f salt. Smaller amounts of salt require longer milling periods while larger amounts give no added advantage and therefore are less economical.

In place of pyridine, there can also be used in this invention, the homologs of pyridine such as quinolines, and alkyl nuclear derivatives, in which the alkyl groups have no more than 10 carbon atoms, preferably no more than 5. For example', quinoline, isoquinoline, methylquinoline, methylpyridine (picoline), ethylpyridine, dimethylpyridine, diethylpyridine, amyl pyridine, octylquinoline, etc. can be used. The pyridine, or homolog is: used in a proportion of OJO-0.32 parts of pyridine, etc. per part of the dichloroquinacridone. Larger amounts can be used but for economic reasons and since no added advantage is derived from larger amounts, the range specified is adequate.

Various types of Vmills can be used for the milling or grinding operation provided that they are equipped for maintaining the desired temperature. It is only necessary that in addition to maintaining the temperature, the mill provides the shearing or attrition necessary to produce the desired particle size. For example, a roller mill or an edge-runner mill or ball mill can be used. Various balls, rolls, nails, etc. are advantageously used in addition to the salt for producing the grinding effect. The grinding time will vary according to the particular type of mill and grinding material used.

It is generally found desirable to mill for at least 15-20 hours depending on the efficiency of the mill. For laboratory size mills generally 24-72 hours is satisfactory, preferably about 48 hours. While no harm is done with excessive amounts of grinding, there is no added advantage in exceeding 72 hours.

While a temperature of .about C. is preferred, the actual temperature can vary to a substantial degree. It has been found that temperatures in the range of 50l00 C. can be used advantageously in producing the new pigment of this invention.

The 4,1l-dichloroquinacridone used for the purpose of this invention can be prepared by heating 2,5-bis(ochloro anilino) terephthalic acid with an alkali metal hydrogen sulfate as described in U.S. Patent 3,107,248.

This product can also be prepared as a mixture of alpha and beta forms as described in U.S. Patent 3,160,510 by the conversion of 2,5-bis(ochloroanilino) terephthalic acid in a manner similar to that described in U.S. Patent 3,264,297 for the preparation of quinacridone by the use of benzoyl chloride and nitrobenzene.

It has also been found by the present inventors that beta-phase 4,11-dichloroquinacridone, or mixtures containing the alpha and beta, can be converted to the alphaphase by heating the material with a methanol solution of KOH. It has also been found that the alpha-phase, or mixtures containing the alpha-phase and beta-phase can be converted to the beta-phase by heating the material with N-methyl pyrrolidone. It has also been found that the 4,1l-dichloroquinacridone can be prepared completely in the alpha-phase by using pyridine also in the benzoyl chloride nitrobenzene preparation referred to above.

The invention is best illustrated by the following examples. These examples are given merely for the purpose of illustration and are not intended in any way to restrict the scope of the invention or the manner in which it can be practiced. Unless specifically provided otherwise, parts and percentages given in the examples and throughout the specification are by weight.

EXAMPLE I A mixture of 1000 g. of 2,5bis(ochloroanilino) terephthalic acid and 5000 cc. of nitrobenzene containing 1010 g. benzoyl chloride is stirred and heated gradually over a period of two hours up to a temperature of 190 C. The mixture is then stirred at 193195 C. for 2l hours, then cooled to G-120 C. and filtered. The orange product is washed with 2.5 liters of nitrobenzene at 100 C., then with 3 liters of cold methanol, and dried with suction. The resultant 4filter cake is stirred for 1-2 hours in 3 liters of methanol and then filtered. The filtrate is again washed with 3 liters of methanol, dried with suction and then in an oven at 125 C. to constant Weight. The 810 grams of orange 4,11-dichloroquinacridone represents a yield of 89% of theoretical. X-ray diffraction analysis shows that this product contains about 55% of the alpha phase and 45% of the beta phase.

Repetition of the foregoing procedure shows a yield as high as 95% can be obtained and the ratio of alpha to beta phase as determined by X-ray analysis can vary from mostly beta to as much as 70% alpha.

EXAMPLE II A 120 gram sample of the product of Example I is reliuxed and stirred for five hours in a solution of 300 grams of potassium hydroxide in 1200 cc. methanol. This suspension is then cooled, filtered and slurried in 3 liters of methanol for one hour. After this is again filtered, the product is washed with another liter of methanol, again slurried in 3 liters of methanol, filtered and washed with one liter of methanol. The resultant orange product is dried to constant weight at 125 C. giving 111.5 grams (93% yield) of almost pure alpha phase 4,1l-dichloroquinacridone as identified by X-ray analysis.

When the foregoing procedure is repeated using a starting material of substantially all beta phase and various mixtures containing various ratios of alpha and beta,

similar results are obtained in converting substantially completely to the alpha phase.

EXAMPLE III A 120 gram sample of the product of Example I is stirred and refiuxed in one liter of N-methylpyrrolidone for 8 hours. The mixture is cooled, filtered, and the filter cake washed with 250 cc. of methanol and then dried with suction. This product is slurried in one liter of methanol for 2 hours, ltered, washed with 250 cc. of additional methanol and dried with suction, and then in an oven at 125 C. to constant weight. The product is orange 4,1l-dichloroquinacridone in the beta phase as identified by X-ray diffraction analysis and in this case there is obtained a yield of 111.3 grams (92.5%). Upon repetition of this procedure, using various mixtures of alpha and beta phases, yields of beta phase up to 98% of theoretical are obtained.

By using the procedures of Examples Il and III to obtain substantially pure alpha and beta phases, various synthetic mixtures can be prepared containing-various ratios of alpha and beta phases.

EXAMPLE IV In the following procedure a ball mill is used cornprising a quart cylindrical steel jar charged with 2,500 grams of Ss inch diameter steel balls or a mixture of 2250 grams of such balls and 250 grams of nails No. 6d, the nails being used to help prevent caking tendencies during milling. The cylindrical jar is 4.5 inches long and 5.5 inches in diameter. This jar is equipped with a lid having a suitable heat-resistant gasket for sealing, preferably a silicone rubber gasket. It is rotated by rollers whose speed is adjustedv so that the rate of rotation is 106 r.p.m. In each experiment, a charge of 20 grams of 4,1l-dichloroquinacridone and 180 grams of dried sodium chloride is used. In each case the sample and the salt together with the mill and grinding medium are stored overnight in a forced draft oven at 100-110" C. tov remove any residual moisture that may be present, The mill is then charged with the sample and the salt. Just prior to sealing the jar, 4.3 parts of pyridine is added.

The milling is carried out for 48 hours at 90 C., the temperature being maintained by having the mill rolls and mill inside an oven maintained at the desired temperature. The charge remains free-flowing during the grinding operation. Upon completion of the milling, the contents of the mill are discharged, and separated from the steel balls by means of a coarse sieve. The milled solid has a bright orange color and weighs 204 grams. This product is dispersed by mixing in a Waring Blendor in 500 ml. of Water for 5 minutes at full speed. The resultant slurry is transferred to a 3000 ml. beaker and agitated by means of a sweep type agitator. To this is added a solution of 52.8 gms. of 98% sulfuric acid in 479 gms. of Water to yield a 5% H2804 .in the slurry, The resultant mixture is heated at -100 C. for 30 minutes after which the solids are filtered on a Buchner funnel and washed to neutrality. The resultant filter cake is dispersed in water by mixing in the Waring Blendor for three minutes in sufficient water to yield a fluid slurry. This slurry is returned to the beaker and water added until the volume is increased to 1000 ml. It is agitated and heated at 95- 100 C. for 15 minutes after which the solids are filtered on a Buchner funnel and washed again with Water. The filter cake thus obtained has a solids content of approximately 30% and is suitable for further processing as desired, i.e. flushing, preparation of dry colors, etc. The yield is 19.3 grams or 96.5% on a 100% solids basis.

Using the above procedure, seven samples of.4,l1di chloroquinacridone having 100%, 85%, 75%, 50%, 25%, 15% and 0% of the alpha phase, with the balance in each case being beta phase, are prepared by mixing the alpha and beta phases produced according to Examples. II and III. In each case, the pigment conditioned according to the above procedure has a new red-orange Vshade and a diffraction spectrum having interplanar spacings in Angstrom units as shown in the table below which'also shows the X-ray diffraction spectra for the alpha and beta phases.

Relative intensity Alpha phase Beta phase New phase Strong lines, A 3 29 I i 7. 3o ef so 4. 02 5. 00 3.92 3. 35 3. 64 14. 50 3. 04 7. 8') 6. 78 6. 2l Weak lines g "z2-" ggg 3. 21 3 12 3. 02

The new red-orange color is analyzed by obtaining trisstimulus data, Munsell renotations, the dominant wave length, and the percent of purity for each sample. The tristimulus data are collected for three levels of pigmentation, namely 100%, 10%, and 1% as diluted ZnO white with the pigment in each case suspended in a varnish as colorless as possible so that it contributes no color. Two parts of varnish are used per part of pigment. These measurements are made by the use of a General Electric Recording Spectrophotometer with a Davidson Hemmendinger Tristimulus Integrator and using as the reference standard a pressed BaSO4 which is manufactured by Bausch and Lomb, Inc.

The spectrophotometer is calibrated for wave length, reectance level-100% line, and internal electronics before the samples are run. From the tristimulus output of the integrator, the chromacity coordinates x and y are calculated by summing the tristimulus values and dividing this into tristimulus X and Y.

The third variable Y is equal to tristimulus Y.

By using the chromacity coordinates in conjunction with a set of charts whiehwc a set of charts which were prepared by the Color Measurement Laboratory of the Agricultural Marketing Administration, USDA, the Munsell Renotations are determined. The data for these charts is based on the Final Report of the O.S.A. Subcommittee on the Spacing of the Munsell Colors, J. Opt. Soc. Am. 33, 1943.

By the use of the book entitled Handbook of Colorimetry by Arthur C. Hardy, The Technology Press M.I.T., Cambridge, Mass., 1936, and these same chromaticity coordinates, the percent purity and the dominant wave length :are determined.

The results obtained from such color analyses of the samples are shown below:

100%I 9.7R 46S/16.34, 02.0% purity (light), 604.5

dom. wave, z=.61$.9; 11:.3495:

EXAMPLE V The procedure of Example I is repeated except that 330 parts of pyridine are added to the benzoyl chloride nitrobenzene mixture prior to the reaction. Instead of obtaining a mixture of alpha and beta as in Example I, the product in this case is entirely the alpha phase as shown by the X-ray diffraction pattern. When this product is used in the procedure of Example IV, either by itself or in various mixtures with beta phase produced in Example III, similar results are obtained as in Example 1V.

When the procedure of Example IV is repeated, varying the proportion of salt from 6 to 15 parts per part of 6 sample, similar results are obtained as in Example IV. Likewise, when temperatures of 60, 75, 85, and 95, respectively, are used, similar results are obtained.

EXAMPLE VI The procedure of Example IV is repeated with similar results using individually in place of the pyridine, quinoline, picoline, dimethylpyridine, ethylpyridine and methyl quinoline.

While certain features of this invention have been described in detail with respect to various embodiments thereof, it Will of course, be apparent that other modifications can be made within the spirit and scope of this invention and it is not intended to limit the invention t0 the exact details show above except insofar as they are defined in the following claims.

The invention claimed is:

1. The process of preparing a new pigment phase of 4,1l-dichloroquinacridone comprising the steps of salt milling 4,1l-dichloroquinacridone with water-soluble inorganic salt, thermally stable and solid at the temperature of salt milling, and selected from the class consisting of ammonia chloride, ammonium sulfate and alkali metal and alkaline earth metal inorganic salts, and a liquid selected from the class consisting of pyridine, quinoline, isoquinoline, methyl quinoline, methyl pyridine, ethyl pyridine, dimethyl pyridine, diethylpyridine, amyl pyridine and octyl quinoline, 0.1 to 0.32 part of said liquid being used per part by weight of said 4,11--dichloroquinacridone at a temperature in the range of 50-100" C. and thereafter separating said pigment from said salt and and said liquid.

2. The process of claim 1 in which said liquid is pyridine.

3. The process of claim 1 in which said salt is sodium chloride.

4. The process of claim 3 in which said sodium chloride is used in an amount of at least 4 parts by weight per part by weight of said pigment.

5. The process of claim 1 in which said temperature is approximately C.

6. The process of claim 1 in which said salt is sodium chloride and said temperature is about 90 C.

7. The process of claim 6 in which said salt is used in an amount of at least 4 parts by weight of said salt per part by weight of said pigment.

8. The process of claim 7 in which said salt milling is conducted for a period of at least 15 hours.

9. The process of claim 2 in which said salt milling is conducted for a period of to at least 15 hours.

References Cited UNITED STATES PATENTS 2,844,581 7/1958 Manger et al. 260-279 3,065,092 11/1962 Geiger et al. 260-314 3,256,285 6/1966 Fuchs et al. 260-279 3,341,345 9/1967 Ehrich 106-288 3,296,008 1/1967 Puain 106-288 2,982,666 5/1961 Chun et al 260-279 DONALD G. DAUS, Primary Examiner U.S. Cl. XR. 

